Binaphthyl-arylamine polymers

ABSTRACT

Disclosed are Binaphthyl-Arylamine Polymers having Formula I: 
                         
In the Formula: Ar 1  is an arylene; Ar 2  is an aryl group; Ar 3  is an arylene; Binap is a binaphthyl moiety; M is a conjugated moiety; and x, y and z are mole fractions such that x+y+z=1.0, with the proviso that x and y are not zero.

RELATED APPLICATION

This application claims priority under 35 U.S.C. §119(e) fromProvisional Application No. 61/119,757 filed on Dec. 4, 2008 which isincorporated by reference in its entirety.

BACKGROUND INFORMATION

1. Field of the Disclosure

The present invention relates to novel electroactive compounds. Theinvention further relates to electronic devices having at least oneactive layer comprising such an electroactive compound.

2. Description of the Related Art

In organic photoactive electronic devices, such as organic lightemitting diodes (“OLED”), that make up OLED displays, the organic activelayer is sandwiched between two electrical contact layers in an OLEDdisplay. In an OLED the organic photoactive layer emits light throughthe light-transmitting electrical contact layer upon application of avoltage across the electrical contact layers.

It is well known to use organic electroluminescent compounds as theactive component in light-emitting diodes. Simple organic molecules,conjugated polymers, and organometallic complexes have been used.Devices that use photoactive materials frequently include one or morecharge transport layers, which are positioned between a photoactive(e.g., light-emitting) layer and a contact layer (hole-injecting contactlayer). A device can contain two or more contact layers. A holetransport layer can be positioned between the photoactive layer and thehole-injecting contact layer. The hole-injecting contact layer may alsobe called the anode. An electron transport layer can be positionedbetween the photoactive layer and the electron-injecting contact layer.The electron-injecting contact layer may also be called the cathode.

There is a continuing need for charge transport materials for use inelectronic devices.

SUMMARY

There is provided a compound having Formula I:

wherein:

-   -   Ar¹ is the same or different at each occurrence and is an        arylene;    -   Ar² is the same or different at each occurrence and is an aryl        group;    -   Ar³ is the same or different at each occurrence and is an        arylene;    -   Binap is a binaphthyl moiety;    -   M is the same or different at each occurrence and is a        conjugated moiety; and    -   x, y and z are mole fractions such that x+y+z=1.0, with the        proviso that x and y are not zero.

There is also provided an electronic device having at least one layercomprising the above compound.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 includes an illustration of one example of an organic electronicdevice.

Skilled artisans appreciate that objects in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the objects in the figures may beexaggerated relative to other objects to help to improve understandingof embodiments.

DETAILED DESCRIPTION

There is provided a compound having Formula I:

wherein:

-   -   Ar¹ is the same or different at each occurrence and is an        arylene;    -   Ar² is the same or different at each occurrence and is an aryl        group;    -   Ar³ is the same or different at each occurrence and is an        arylene;    -   Binap is a binaphthyl moiety;    -   M is the same or different at each occurrence and is a        conjugated moiety; and    -   x, y and z are mole fractions such that x+y+z=1.0, with the        proviso that x and y are not zero.

There is also provided an electronic device having at least one layercomprising a compound having Formula I.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims. The detailed description first addresses Definitions andClarification of Terms followed by the Electroactive Compound, theElectronic Device, and finally Examples.

1. DEFINITIONS AND CLARIFICATION OF TERMS

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein, the term “alkyl” includes branched and straight-chainsaturated aliphatic hydrocarbon groups. Unless otherwise indicated, theterm is also intended to include cyclic groups. Examples of alkyl groupsinclude methyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, tertbutyl,pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyland the like. The term “alkyl” further includes both substituted andunsubstituted hydrocarbon groups. In some embodiments, the alkyl groupmay be mono-, di- and tri-substituted. One example of a substitutedalkyl group is trifluoromethyl. Other substituted alkyl groups areformed from one or more of the substituents described herein. In certainembodiments alkyl groups have 1 to 20 carbon atoms. In otherembodiments, the group has 1 to 6 carbon atoms. The term is intended toinclude heteroalkyl groups. Heteroalkyl groups may have from 1-20 carbonatoms.

The term “aryl” means an aromatic carbocyclic moiety, which may be asingle ring (monocyclic) or multiple rings (bicyclic, or more) fusedtogether or linked covalently. Any suitable ring position of the arylmoiety may be covalently linked to the defined chemical structure.Examples of aryl moieties include, but are not limited to, phenyl,1-naphthyl, 2-naphthyl, dihydronaphthyl, tetrahydronaphthyl, biphenyl,anthryl, phenanthryl, fluorenyl, indanyl, biphenylenyl, acenaphthenyl,acenaphthylenyl, and the like. In some embodiments, aryl groups have 6to 60 carbon atoms; in some embodiments 6 to 48 carbon atoms. The termis intended to include heteroaryl groups. Heteroaryl groups may havefrom 4-50 carbon atoms.

The term “alkoxy” is intended to mean the group —OR, where R is alkyl.

The term “aryloxy” is intended to mean the group —OR, where R is aryl.

Unless otherwise indicated, all groups can be substituted orunsubstituted. An optionally substituted group, such as, but not limitedto, alkyl or aryl, may be substituted with one or more substituentswhich may be the same or different. Suitable substituents include alkyl,aryl, nitro, cyano, —N(R⁷)(R⁸), halo, hydroxy, carboxy, alkenyl,alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy,alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl,siloxane, thioalkoxy, —S(O)₂—N(R′)(R″), —C(═O)—N(R)(R″),(R′)(R″)N-alkyl, (R′)(R″)N-alkoxyalkyl, (R′)(R″)N-alkylaryloxyalkyl,—S(O)_(s)-aryl (where s=0-2) or —S(O)_(s)-heteroaryl (where s=0-2). EachR′ and R″ is independently an optionally substituted alkyl, cycloalkyl,or aryl group. R′ and R″, together with the nitrogen atom to which theyare bound, can form a ring system in certain embodiments. Substituentsmay also be crosslinking groups.

The term “charge transport,” when referring to a layer, material,member, or structure is intended to mean such layer, material, member,or structure facilitates migration of such charge through the thicknessof such layer, material, member, or structure with relative efficiencyand small loss of charge. Hole transport materials facilitate positivecharge; electron transport material facilitate negative charge. Althoughlight-emitting materials may also have some charge transport properties,the term “charge transport layer, material, member, or structure” is notintended to include a layer, material, member, or structure whoseprimary function is light emission.

The term “compound” is intended to mean an electrically unchargedsubstance made up of molecules that further include atoms, wherein theatoms cannot be separated from their corresponding molecules by physicalmeans without breaking chemical bonds. The term is intended to includeoligomers and polymers.

The term “crosslinkable group” or “crosslinking group” is intended tomean a group than can lead to crosslinking via thermal treatment orexposure to radiation. In some embodiments, the radiation is UV orvisible.

The term “electroactive” as it refers to a layer or a material, isintended to indicate a layer or material which electronicallyfacilitates the operation of an electronic device. Examples ofelectroactive materials include, but are not limited to, materials whichconduct, inject, transport, or block a charge, where the charge can beeither an electron or a hole, or materials which emit radiation orexhibit a change in concentration of electron-hole pairs when receivingradiation. Examples of inactive materials include, but are not limitedto, planarization materials, insulating materials, and environmentalbarrier materials.

The prefix “fluoro” is intended to indicate that one or more hydrogensin a group has been replaced with fluorine.

The prefix “hetero” indicates that one or more carbon atoms has beenreplaced with a different atom. In some embodiments, the heteroatom isO, N, S, or combinations thereof.

The term “oxyalkyl” is intended to mean a heteroalkyl group having oneor more carbons replaced with oxygens. The term includes groups whichare linked via an oxygen.

The term “photoactive” is intended to mean to any material that exhibitselectroluminescence or photosensitivity.

The term “silyl” refers to the group R₃Si—, where R is H, D, C1-20alkyl, fluoroalkyl, or aryl. In some embodiments, one or more carbons inan R alkyl group are replaced with Si. In some embodiments, the silylgroups are (hexyl)₂Si(Me)CH₂CH₂Si(Me)₂— and [CF₃(CF₂)₆CH₂CH₂]₂SiMe—.

The term “siloxane” refers to the group (RO)₃Si—, where R is H, D, C1-20alkyl, or fluoroalkyl.

The phrase “adjacent to,” when used to refer to layers in a device, doesnot necessarily mean that one layer is immediately next to anotherlayer. On the other hand, the phrase “adjacent R groups,” is used torefer to R groups that are next to each other in a chemical formula(i.e., R groups that are on atoms joined by a bond).

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in textbooks and other sources within the organic light-emittingdiode display, photodetector, photovoltaic, and semiconductive memberarts.

2. ELECTROACTIVE COMPOUND

The compound described herein has Formula I:

wherein:

-   -   Ar¹ is the same or different at each occurrence and is an        arylene;    -   Ar² is the same or different at each occurrence and is an aryl        group;    -   Ar³ is the same or different at each occurrence and is an        arylene;    -   Binap is a binaphthyl moiety;    -   M is the same or different at each occurrence and is a        conjugated moiety; and    -   x, y and z are mole fractions such that x+y+z=1.0, with the        proviso that x and y are not zero.

The compounds of Formula I have at least a binaphthyl moiety and an arylamino moiety having two amino nitrogens. The compounds have good holetransport properties. When these materials are used in the holetransport layer of OLEDs, the resulting devices can have good efficiencyand lifetime. In some embodiments, the compounds can be used as hostsfor light-emitting materials in light-emitting layers of devices.

In some embodiments, the Binap group is a 1,1′-binaphthyl group havingFormula II

where:

-   -   * represents a point of attachment to the other units in the        compound;    -   R¹ is the same or different at each occurrence and is selected        from the group consisting of H, D, aryl groups, alkyl groups,        silyl groups, siloxane groups, fluoroalkyl groups, alkoxy        groups, and fluoroalkoxy groups, or the two R¹ groups may be        joined together to form an aliphatic ring having 5-10 carbons;    -   R² is the same or different at each occurrence and is selected        from the group consisting of D, aryl groups, alkyl groups, silyl        groups, siloxane groups, fluoroalkyl groups, alkoxy groups, and        fluoroalkoxy groups; and    -   a is the same or different at each occurrence and is an integer        from 0-5.

In some embodiments, the 1,1′-binaphthyl group has Formula IIa withpoints of attachment at the 3- and 3′-positions, where *, R¹, R² and aare as defined above:

As used herein, the structure indicates that R² can be bonded to any ofavailable carbons in the fused ring structure.

In some embodiments, the 1,1′-binaphthyl group has Formula IIb withpoints of attachment at the 4- and 4′-positions, where *, R¹, R² and aare as defined above:

In some embodiments, the 1,1′-binaphthyl group has Formula IIc withpoints of attachment at the 5- and 5′-positions, where *, R¹, R² and aare as defined above:

In some embodiments, the 1,1′-binaphthyl group has Formula IId withpoints of attachment at the 6- and 6′-positions, where *, R¹, R² and aare as defined above:

In some embodiments, the 1,1′-binaphthyl group has Formula IIe withpoints of attachment at the 7- and 7′-positions, where *, R¹, R² and aare as defined above:

In some embodiments of Formulae II and IIa-e, R¹ is selected from analkyl group having 1-12 carbon atoms and an alkoxy group having 1-12carbon atoms.

In some embodiments of Formulae II and IIa-e, R² is selected an alkylgroup having 1-12 carbon atoms and an alkoxy group having 1-12 carbonatoms.

In some embodiments of Formulae II and IIa-e, a is selected from 0and 1. In some embodiments, a=0.

In some embodiments, Ar¹ has Formula III

where:

-   -   R³ is the same or different at each occurrence and is selected        from the group consisting of D, alkyl, alkoxy, siloxane and        silyl;    -   c is the same or different at each occurrence and is an integer        from 0-4; and    -   m is the same or different at each occurrence and is an integer        from 1 to 6.        In some embodiments, at least one of one c is not zero. In some        embodiments, m=1-3.

In some embodiments, Ar¹ is selected from the group consisting ofphenylene, p-biphenylene, p-terphenylene, naphthylene,phenylenenaphthylene, and naphthylenephenylene. In some embodiments, Ar¹is selected from the group consisting of phenylene and biphenylene.

In some embodiments, Ar² has Formula IV

where:

-   -   R³ is the same or different at each occurrence and is selected        from the group consisting of D, alkyl, alkoxy, siloxane and        silyl;    -   c is the same or different at each occurrence and is an integer        from 0-4;    -   d is the same or different at each occurrence and is an integer        from 0-5; and    -   m is the same or different at each occurrence and is an integer        from 1 to 6.

In some embodiments of Formula IV, at least one of one c and d is notzero. In some embodiments, m=1-3. In some embodiments, Ar² is selectedfrom the group consisting phenyl, biphenyl, terphenyl, and naphthyl.

In some embodiments, Ar³ has Formula III, as defined above. In someembodiments of Formula III, at least one of one c and d is not zero. Insome embodiments, m=1-3. In some embodiments, Ar³ is selected from thegroup consisting of phenylene, biphenylene, and naphthylene. In someembodiments, Ar³ is selected from the group consisting of phenylene andbiphenylene.

Any of Ar¹, Ar² and Ar³ may be substituted at any position. Thesubstituents may be present to improve one or more physical propertiesof the compound, such as solubility. In some embodiments, thesubstituents are selected from the group consisting of D, alkyl groups,silyl groups, siloxane groups, and alkoxy groups. In some embodiments,the groups have from 1-12 carbon atoms. In some embodiments, adjacentalkyl groups are joined together to form a non-aromatic ring. In someembodiments, there is at least one substituent which includes acrosslinkable group. In some embodiments, crosslinking substituents arepresent on at least one Ar². Examples of crosslinkable groups include,but are not limited to vinyl, acrylate, perfluorovinylether,1-benzo-3,4-cyclobutane, siloxane, cyanate groups, cyclic ethers(epoxides), cycloalkenes, and acetylenic groups. In one embodiment, thecrosslinkable group is vinyl.

Formula I represents a copolymer in which there is at least twodifferent conjugated moieties. In some embodiments, x is at least 0.4and y is at least 0.4. In some embodiments, x and y are each in therange of 0.4 to 0.6. The copolymers can be random, alternating, or blockcopolymers. In some embodiments, the copolymers are random.

In some embodiments, z is greater than 0 and M is an aromatic unithaving triarylamine units. In some embodiments, M is an aromatic group.In some embodiments, M is an aromatic unit having a crosslinkablesubstituent. The amount of M having a crosslinkable substituent isgenerally between 4 and 20 mole percent.

When the Binap group has Formula II and R¹ is not H or D, thesubstituted binaphthyl group introduces non-planarity into the backboneof the compound having Formula I. The first naphthyl group is orientedin a plane that is different from the second naphthyl group to which itis linked. Because of the non-planarity, the compounds are chiral. Ingeneral, they are formed as racemic mixtures.

Some non-limiting examples of compounds having Formula I includeCompounds A to C below.

The new compounds can be made using any technique that will yield a C—Cor C—N bond. A variety of such techniques are known, such as Suzuki,Yamamoto, Stille, and other transition metal catalyzed couplingreactions. The compounds can be formed into layers using solutionprocessing techniques. The term “layer” is used interchangeably with theterm “film” and refers to a coating covering a desired area. The term isnot limited by size. The area can be as large as an entire device or assmall as a specific functional area such as the actual visual display,or as small as a single sub-pixel. Layers and films can be formed by anyconventional deposition technique, including vapor deposition, liquiddeposition (continuous and discontinuous techniques), and thermaltransfer. Continuous deposition techniques, include but are not limitedto, spin coating, gravure coating, curtain coating, dip coating,slot-die coating, spray coating, and continuous nozzle coating.Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing. When crosslinkinggroups are present, the films can be heated and/or treated with UV lightto form crosslinked films. The crosslinked films are more robust toadditional processing steps and generally are not soluble in processingsolvents.

The new compounds described herein have can be used as hole transportmaterials, as photoactive materials, and as hosts for photoactivematerials. The new compounds have hole mobilities and HOMO/LUMO energiessimilar to efficient small molecule hole transport compounds such asN,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD) and N,N′-bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB).Compounds such as TPD and NPD generally must be applied using a vapordeposition technique.

In some embodiments, the new compounds are useful as hosts forphotoactive materials.

3. ELECTRONIC DEVICES

Organic electronic devices that may benefit from having one or morelayers comprising at least one compound as described herein include, butare not limited to, (1) devices that convert electrical energy intoradiation (e.g., a light-emitting diode, light emitting diode display,or diode laser), (2) devices that detect signals through electronicsprocesses (e.g., photodetectors, photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes, IR detectors), (3) devicesthat convert radiation into electrical energy, (e.g., a photovoltaicdevice or solar cell), and (4) devices that include one or moreelectronic components that include one or more organic semi-conductorlayers (e.g., a transistor or diode). Other uses for the compositionsaccording to the present invention include coating materials for memorystorage devices, antistatic films, biosensors, electrochromic devices,solid electrolyte capacitors, energy storage devices such as arechargeable battery, and electromagnetic shielding applications.

One illustration of an organic electronic device structure is shown inFIG. 1. The device 100 has an anode layer 110 and a cathode layer 150,and a photoactive layer 130 between them. Adjacent to the anode is alayer 120 comprising a charge transport material, for example, a holetransport material. Adjacent to the cathode may be a charge transportlayer 140 comprising an electron transport material. As an option,devices may use one or more additional hole injection or hole transportlayers (not shown) next to the anode 110 and/or one or more additionalelectron injection or electron transport layers (not shown) next to thecathode 150.

As used herein, the term “photoactive” refers to a material that emitslight when activated by an applied voltage (such as in a light-emittingdiode or light-emitting electrochemical cell), or responds to radiantenergy and generates a signal with or without an applied bias voltage(such as in a photodetector). In one embodiment, a photoactive layer isan emitter layer.

Depending upon the application of the device 100, the photoactive layer130 can be a light-emitting layer that is activated by an appliedvoltage (such as in a light-emitting diode or light-emittingelectrochemical cell), a layer of material that responds to radiantenergy and generates a signal with or without an applied bias voltage(such as in a photodetector). Examples of photodetectors includephotoconductive cells, photoresistors, photoswitches, phototransistors,and phototubes, and photovoltaic cells, as these terms are described inKirk-Othmer Concise Encyclopedia of Chemical Technology, 4^(th) edition,p. 1537, (1999). In some embodiments, the hole transport layer 120comprises at least one new electroactive compound as described herein.

In some embodiments, the photoactive layer 130 comprises at least onenew electroactive compound as described herein, wherein theelectroactive compound is photoactive.

In some embodiments, the photoactive layer 130 comprises at least onenew electroactive compound as described herein, wherein theelectroactive compound serves as a host having a photoactive materialdispersed therein.

The other layers in the device can be made of any materials which areknown to be useful in such layers. The anode 110, is an electrode thatis particularly efficient for injecting positive charge carriers. It canbe made of, for example materials containing a metal, mixed metal,alloy, metal oxide or mixed-metal oxide, or it can be a conductingpolymer, and mixtures thereof. Suitable metals include the Group 11metals, the metals in Groups 4, 5, and 6, and the Group 8 10 transitionmetals. If the anode is to be light-transmitting, mixed-metal oxides ofGroups 12, 13 and 14 metals, such as indium-tin-oxide, are generallyused. The anode 110 may also comprise an organic material such aspolyaniline as described in “Flexible light-emitting diodes made fromsoluble conducting polymer,” Nature vol. 357, pp 477 479 (11 Jun. 1992).At least one of the anode and cathode should be at least partiallytransparent to allow the generated light to be observed.

In some embodiments, the device further comprises a buffer layer betweenthe anode and the layer comprising the new polymer. The term “bufferlayer” is intended to mean a layer comprising electrically conductive orsemiconductive materials and may have one or more functions in anorganic electronic device, including but not limited to, planarizationof the underlying layer, charge transport and/or charge injectionproperties, scavenging of impurities such as oxygen or metal ions, andother aspects to facilitate or to improve the performance of the organicelectronic device. Buffer materials may be polymers, oligomers, or smallmolecules, and may be in the form of solutions, dispersions,suspensions, emulsions, colloidal mixtures, or other compositions. Thebuffer layer can be formed with polymeric materials, such as polyaniline(PANI) or polyethylenedioxythiophene (PEDOT), which are often doped withprotonic acids. The protonic acids can be, for example,poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonicacid), and the like. The buffer layer can comprise charge transfercompounds, and the like, such as copper phthalocyanine and thetetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In oneembodiment, the buffer layer is made from a dispersion of a conductingpolymer and a colloid-forming polymeric acid. Such materials have beendescribed in, for example, published U.S. patent applications2004-0102577, 2004-0127637, and 2005/205860.

In some embodiments, hole transport layer 120 comprises the newelectroactive compound described herein. In some embodiments, layer 120comprises other hole transport materials. Examples of other holetransport materials for layer 120 have been summarized for example, inKirk Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol.18, p. 837 860, 1996, by Y. Wang. Both hole transporting molecules andpolymers can be used. Commonly used hole transporting molecules include,but are not limited to:N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD), 1,1-bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD), tetrakis (3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl 4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine (TPA), bis[4(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB),N,N,N′,N′ tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),N,N′-Bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB), andporphyrinic compounds, such as copper phthalocyanine. Commonly used holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, and polyaniline. It isalso possible to obtain hole transporting polymers by doping holetransporting molecules such as those mentioned above into polymers suchas polystyrene and polycarbonate. Buffer layers and/or hole transportlayer can also comprise polymers of thiophene, aniline, or pyrrole withpolymeric fluorinated sulfonic acids, as described in published USapplications 2004/102577, 2004/127637, and 2005/205860.

Any organic electroluminescent (“EL”) material can be used as thephotoactive material in layer 130, including, but not limited to, smallmolecule organic fluorescent compounds, fluorescent and phosphorescentmetal complexes, conjugated polymers, and mixtures thereof. Examples offluorescent compounds include, but are not limited to, chrysenes,pyrenes, perylenes, rubrenes, coumarins, anthracenes, thiadiazoles,derivatives thereof, and mixtures thereof. Examples of metal complexesinclude, but are not limited to, metal chelated oxinoid compounds, suchas tris(8-hydroxyquinolato)aluminum (Alq3); cyclometalated iridium andplatinum electroluminescent compounds, such as complexes of iridium withphenylpyridine, phenylquinoline, or phenylpyrimidine ligands asdisclosed in Petrov et al., U.S. Pat. No. 6,670,645 and Published PCTApplications WO 03/063555 and WO 2004/016710, and organometalliccomplexes described in, for example, Published PCT Applications WO03/008424, WO 03/091688, and WO 03/040257, and mixtures thereof. In somecases the small molecule fluorescent or organometallic materials aredeposited as a dopant with a host material to improve processing and/orelectronic properties. Examples of conjugated polymers include, but arenot limited to poly(phenylenevinylenes), polyfluorenes,poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymersthereof, and mixtures thereof. The materials may also be present inadmixture with a host material. In some embodiments, the host materialis a hole transport material or an electron transport material. In someembodiments, the host is the new electroactive compound describedherein. In some embodiments, the ratio of host material to photoactivematerial is in the range of 5:1 to 20:1; in some embodiments, 10:1 to15:1. Examples of electron transport materials which can be used in theelectron transport layer 140 and/or the optional layer between layer 140and the cathode include metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (AlQ),bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum (BAlq),tetrakis-(8-hydroxyquinolato)hafnium (HfQ) andtetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds suchas 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivativessuch as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthrolines such as4,7-diphenyl-1,10-phenanthroline (DPA) and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and mixturesthereof.

The cathode 150, is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode can be anymetal or nonmetal having a lower work function than the anode. Materialsfor the cathode can be selected from alkali metals of Group 1 (e.g., Li,Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, includingthe rare earth elements and lanthanides, and the actinides. Materialssuch as aluminum, indium, calcium, barium, samarium and magnesium, aswell as combinations, can be used. Li-containing organometalliccompounds, LiF, and Li₂O can also be deposited between the organic layerand the cathode layer to lower the operating voltage.

The choice of materials for each of the component layers is preferablydetermined by balancing the goals of providing a device with high deviceefficiency with device operational lifetime. Other layers may also bepresent in the device. There may be one or more hole injection and/orhole transport layers between the buffer layer and the organic activelayer. There may be one or more electron transport layers and/orelectron injection layers between the organic active layer and thecathode.

The device can be prepared by a variety of techniques, includingsequentially depositing the individual layers on a suitable substrate.Substrates such as glass and polymeric films can be used. Conventionalvapor deposition techniques can be used, such as thermal evaporation,chemical vapor deposition, and the like. Alternatively, the organiclayers can be applied by liquid deposition using suitable solvents. Theliquid can be in the form of solutions, dispersions, or emulsions.Typical liquid deposition techniques include, but are not limited to,continuous deposition techniques such as spin coating, gravure coating,curtain coating, dip coating, slot-die coating, spray-coating, andcontinuous nozzle coating; and discontinuous deposition techniques suchas ink jet printing, gravure printing, and screen printing, anyconventional coating or printing technique, including but not limited tospin-coating, dip-coating, roll-to-roll techniques, ink jet printing,screen-printing, gravure printing and the like.

The new electroactive compounds described herein can be applied byliquid deposition from a liquid composition. The term “liquidcomposition” is intended to mean a liquid medium in which a material isdissolved to form a solution, a liquid medium in which a material isdispersed to form a dispersion, or a liquid medium in which a materialis suspended to form a suspension or an emulsion. Any liquid medium inwhich the compound is dissolved or dispersed and from which it will forma film can be used. In one embodiment, the liquid medium consistsessentially of one or more organic solvents. In one embodiment theorganic solvent is an aromatic solvent. In one embodiment, the organicliquid is selected from chloroform, dichloromethane, toluene, anisole,and mixtures thereof. The new compound can be present in the liquidmedium in a concentration of 0.2 to 2 percent by weight. Other weightpercentages of the new compound may be used depending upon the liquidmedium.

In one embodiment, the different layers have the following range ofthicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000 Å; holetransport layer 120, 50-2000 Å, in one embodiment 200-1000 Å;photoactive layer 130, 10-2000 Å, in one embodiment 100-1000 Å; layer140, 50-2000 Å, in one embodiment 100-1000 Å; cathode 150, 200-10000 Å,in one embodiment 300-5000 Å. The location of the electron-holerecombination zone in the device, and thus the emission spectrum of thedevice, can be affected by the relative thickness of each layer. Thusthe thickness of the electron-transport layer should be chosen so thatthe electron-hole recombination zone is in the light-emitting layer. Thedesired ratio of layer thicknesses will depend on the exact nature ofthe materials used.

In one embodiment, the device has the following structure, in order:anode, buffer layer, hole transport layer, photoactive layer, electrontransport layer, electron injection layer, cathode. In one embodiment,the anode is made of indium tin oxide or indium zinc oxide. In oneembodiment, the buffer layer comprises a conducting polymer selectedfrom the group consisting of polythiophenes, polyanilines, polypyrroles,copolymers thereof, and mixtures thereof. In one embodiment, the bufferlayer comprises a complex of a conducting polymer and a colloid-formingpolymeric acid.

In one embodiment, the hole transport layer comprises the new compounddescribed herein. In one embodiment, the hole transport layer consistsessentially of the new electroactive compound described herein.

In one embodiment, the photoactive layer comprises the new electroactivecompound described herein and a photoactive compound. In one embodiment,the photoactive layer further comprises a second host material. In someembodiments, the photoactive layer consists essentially of the newelectroactive compound described herein and a photoactive compound. Insome embodiments, the photoactive material is present in an amount of atleast 1% by weight. In some embodiments, the photoactive material is2-20% by weight.

In one embodiment, the electron transport layer comprises a metalcomplex of a hydroxyaryl-N-heterocycle. In one embodiment, thehydroxyaryl-N-heterocycle is unsubstituted or substituted8-hydroxyquinoline.

In one embodiment, the electron injection layer is LiF or Li₂O. In oneembodiment, the cathode is Al or Ba/Al.

In one embodiment, the device is fabricated by liquid deposition of thebuffer layer, the hole transport layer, and the photoactive layer, andby vapor deposition of the electron transport layer, the electroninjection layer, and the cathode.

Although methods and materials similar or equivalent to those describedherein can be used in the practice or testing of the present invention,suitable methods and materials are described below. In addition, thematerials, methods, and examples are illustrative only and not intendedto be limiting. All publications, patent applications, patents, andother references mentioned herein are incorporated by reference in theirentirety.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

This example illustrates the preparation of a binaphthyl monomer, asoutlined below. The monomer can be used to form an electroactivecompound, Compound A.

(a) The starting material ditriflate 1 was synthesized from the schemedescribed below.

Compound 4 was synthesized from 7-methoxy-2-naphthol by following theliterature method as described in Tetrahedron Letters (Masahiro Noji,Makoto Nakajima, Kenji Koga, vol. 35, No. 43, pp 7983-7984, 1994).

Compound 5:

To the solution of compound 4 (3.9 g, 11.26 mmol) in pyridine (40 mL)was slowly added Tf₂O (6.98 g, 24.77 mmol, 2.2 eq) at −10° C. Themixture was stirred for 6 h as the temperature rose to room temperature.The mixture was diluted with ethyl acetate, followed by the washing withwater and brine successively. The organic layer was dried over anhydrousMgSO₄. Filtration, concentration of the filtrate, and short silicacolumn provided a desired material 5 (6.5 g).

Compound 6:

To the solution of compound 5 (6.3 g, 10.32 mmol) in ether (25 mL) wasadded MeMgBr (3M in ether, 25 mL, 75.33 mmol), followed by the catalystNi(DPPP)Cl₂ (0.28 g, 0.516 mmol). The mixture was stirred at rt for 24 hunder nitrogen, and then quenched with isopropanol. The mixture wastreated with ethyl acetate and water, followed by the addition of 1 MHCl (20 mL). The organic layer was dried over anhydrous MgSO₄.Filtration, concentration of the filtrate, and short silica columnprovided a desired material 6 (3.2 g).

Compound 7:

To the solution of compound 6 (3 g, 8.76 mmol) in methylene chloride (40mL) was added BBr₃ (1M in methylene chloride, 19 mL, 18.4 mmol) at 0° C.under nitrogen. The mixture was stirred at rt for 24 h under nitrogen,and then quenched with water. The mixture was diluted with methylenechloride, and then washed with water. The organic layer was dried overanhydrous MgSO₄. Filtration, concentration of the filtrate, and shortsilica column provided a desired material 7 (2.75 g).

Compound 8:

To the solution of compound 7 (2.75 g, 8.74 mmol) in pyridine (40 mL)was slowly added Tf₂O (5.43 g, 19.24 mmol, 2.2 eq) at −10° C. Themixture was stirred for 6 h as the temperature rose to room temperature.The mixture was diluted with ethyl acetate, followed by the washing withwater and brine successively. The organic layer was dried over anhydrousMgSO₄. Filtration, concentration of the filtrate, and short silicacolumn provided a desired material 8 (5.0 g).

Compound 9: Compound 8 (10 g, 17.28 mmol), 3-methoxyphenyl boronic acid(6.56 g, 43.21 mmol, 2.5 eq), and the catalyst (palladium tetrakistriphenylphosphine) (2 g, 0.17 mmol) were mixed together in a degassedTHF (90 mL) under nitrogen, followed by the addition of a degassedsolution of Na₂CO₃ (9.16 g, 86.43 mmol, 5 eq) in 70 ml water. Thereaction mixture was heated to reflux for 24 hrs, and then the mixturewas treated with methylene chloride and water. The organic layer wasdried with MgSO₄, filtered, and concentrated. By column chromatography(7% EtOAc in hexane) the desired material 9 (8.55 g) was obtained as awhite solid.

Compound 1: To the solution of compound 9 (8.55 g, 17.28 mmol) inmethylene chloride (80 mL) was added BBr₃ (1 M in methylene chloride,36.3 mL, 36.3 mmol) at 0° C. under nitrogen. The mixture was stirred atrt for 16 h under nitrogen, and then quenched with water. The mixturewas diluted with methylene chloride, and then washed with water. Theorganic layer was dried over anhydrous Na₂SO₄ Filtration, concentrationof the filtrate, and short silica column provided a desired diolcompound (9.08 g). To the solution of this diol compound (8.07 g, 17.3mmol) in pyridine (100 mL) was slowly added Tf₂O (10.74 g, 38.05 mmol,2.2 eq) at −10° C. The mixture was stirred for 20 h as the temperaturerose to room temperature. The mixture was diluted with ethyl acetate,followed by the washing with water and brine successively. The organiclayer was dried over anhydrous Na₂SO₄ Filtration, concentration of thefiltrate, and silica column chromatography (10% to 20% methylenechloride in hexane) provided a desired material 1 (11.1 g) as a whitesolid.

(b) The monomer 3 was synthesized according to the scheme below.

In a nitrogen purged glove box, ditriflate 1 (3 g, 4.11 mmol) and3-octylaniline (1.77 g, 8.62 mmol) were dissolved in toluene (40 mL) ina 100 mL of round bottom flask, followed by the addition of the toluene(10 mL) solution of tris(dibenzylideneacetone)dipalladium(0) (102 mg,0.027 eq.) and 1,1′-bis(diphenylphosphino)ferrocene (121 mg, 0.053 eq)to the mixture. After stirring the mixture for 5 min, sodium t-butoxide(0.986 g, 10.26 mmol, 2.5 eq) was added to the resultant solution. Thereaction mixture was stirred for 3 days at 85° C. under nitrogen outsideglove box. The mixture was passed through a pad of silica gel, which wasrinsed with toluene. The combined solution was concentrated on a rotaryevaporator, followed by flash column chromatography (5% to 10%ethylacetate in hexane, gradiently) to afford 3 g of a white solid as aproduct. NMR analysis confirmed the structure of intermediate diaminecompound 2.

In a nitrogen purged glove box, diamine 2 (1.2 g, 1.42 mmol) and4-bromo-4′-iodobiphenyl (2.3 g, 6.42 mmol) were dissolved in toluene (30mL) in a 100 mL of round bottom flask, followed by the addition of thetoluene (8 mL) solution of tris(dibenzylideneacetone)dipalladium(0) (35mg, 0.027 eq.) and 1,1′-bis(diphenylphosphino)ferrocene (42 mg, 0.053eq) to the mixture. After stirring the mixture for 5 min, sodiumt-butoxide (341 mg, 3.55 mmol, 2.5 eq) was added to the resultantsolution. The reaction mixture was stirred for 20 h at 95° C. undernitrogen outside glove box. The mixture was passed through a pad ofsilica gel, which was rinsed with toluene. The combined solution wasconcentrated on a rotary evaporator, followed by flash columnchromatography (7% toluene in hexane) to afford 1.2 g of a white solid.NMR analysis confirmed the structure of compound 3.

Example 2

The monomer from Example 1 can be polymerized in a 1:1 molar ratio withN,N′-bis(4-bromophenyl)-N,N′-diphenylbenzidine to form Compound A. Thiscan be done using Yamamoto coupling according to the following scheme:

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges include each and everyvalue within that range.

What is claimed is:
 1. A copolymer having Formula I:

wherein: M is the same or different at each occurrence and is selectedfrom the group consisting of an aromatic unit having triarylamine unitsand an aromatic unit having a crosslinkable substituent; and x, y and zare mole fractions such that x+y+z=1.0, with the proviso that x and yare not zero; wherein Binap is a 1,1′-binaphthyl group having a formulaselected from the group consisting of Formula IIa, Formula IIc, FormulaIId, and Formula IIe

where: * represents a point of attachment to the other units in thecompound; R¹ is the same or different at each occurrence and is selectedfrom the group consisting of H, D, aryl groups, alkyl groups, silylgroups, siloxane groups, fluoroalkyl groups, alkoxy groups, andfluoroalkoxy groups, or the two R¹ groups may be joined together to forman aliphatic ring having 5-10 carbons; R² is the same or different ateach occurrence and is selected from the group consisting of D, arylgroups, alkyl groups, silyl groups, siloxane groups, fluoroalkyl groups,alkoxy groups, and fluoroalkoxy groups; and a is the same or differentat each occurrence and is an integer from 0-5; wherein Ar¹ is selectedfrom the group consisting of phenylene, p-biphenylene, p-terphenylene,naphthylene, phenylenenaphthylene, naphthylenephenylene and a grouphaving Formula III

where: R³ is the same or different at each occurrence and is selectedfrom the group consisting of D, alkyl, alkoxy, siloxane and silyl; c isthe same or different at each occurrence and is an integer from 0-4; andm is the same or different at each occurrence and is an integer from 1to 6; wherein Ar² is selected from the group consisting of naphthyl anda group having Formula IV

where: d is the same or different at each occurrence and is an integerfrom 0-5; and wherein Ar³ is selected from the group consisting ofnaphthylene and a group having Formula III.
 2. The copolymer of claim 1,wherein R¹ is selected from an alkyl group having 1-12 carbon atoms andan alkoxy group having 1-12 carbon atoms.
 3. The copolymer of claim 1,wherein R² is selected from an alkyl group having 1-12 carbon atoms andan alkoxy group having 1-12 carbon atoms.
 4. The copolymer of claim 1,wherein crosslinking substituents are present on at least one Ar². 5.The copolymer of claim 1, wherein x and y are each in the range of 0.4to 0.6.
 6. The copolymer of claim 1, wherein z is not zero.
 7. Anorganic electronic device comprising a first electrical contact layer, asecond electrical contact layer and an active layer therebetween,wherein the active layer comprises a copolymer having Formula I:

wherein: M is the same or different at each occurrence and is selectedfrom the group consisting of an aromatic unit having triarylamine unitsand an aromatic unit having a crosslinkable substituent; and x, y and zare mole fractions such that x+y+z=1.0, with the proviso that x and yare not zero; wherein Binap is a 1,1′-binaphthyl group having a formulaselected from the group consisting of Formula IIa, Formula IIc, FormulaIId, and Formula IIe

where: * represents a point of attachment to the other units in thecompound; R¹ is the same or different at each occurrence and is selectedfrom the group consisting of H, D, aryl groups, alkyl groups, silylgroups, siloxane groups, fluoroalkyl groups, alkoxy groups, andfluoroalkoxy groups, or the two R¹ groups may be ioined together to forman aliphatic ring having 5-10 carbons; R² is the same or different ateach occurrence and is selected from the group consisting of D, arylgroups, alkyl groups, silyl groups, siloxane groups, fluoroalkyl groups,alkoxy groups, and fluoroalkoxy groups; and a is the same or differentat each occurrence and is an integer from 0-5; wherein Ar¹ is selectedfrom the group consisting of phenylene, p-biphenylene, p-terphenylene,naphthylene, phenylenenaphthylene, naphthylenephenylene and a grouphaving Formula III

where: R³ is the same or different at each occurrence and is selectedfrom the group consisting of D, alkyl, alkoxy, siloxane and silyl; c isthe same or different at each occurrence and is an integer from 0-4; andm is the same or different at each occurrence and is an integer from 1to 6; wherein Ar² is selected from the group consisting of naphthyl anda group having Formula IV

where: d is the same or different at each occurrence and is an integerfrom 0-5; and wherein Ar³ is selected from the group consisting ofnaphthylene and a group having Formula III.
 8. The device of claim 7,wherein R¹ is selected from an alkyl group having 1-12 carbon atoms andan alkoxy group having 1-12 carbon atoms.
 9. The device of claim 7,wherein R² is selected an alkyl group having 1-12 carbon atoms and analkoxy group having 1-12 carbon atoms.
 10. The device of claim 7,wherein a crosslinking substituent is present on at least one Ar². 11.The device of claim 7, wherein x and y are each in the range of 0.4 to0.6.
 12. The device of claim 7, wherein z is not zero.
 13. The device ofclaim 7, wherein the active layer is a hole transport layer and thelayer consists essentially of a copolymer having Formula I.
 14. Thedevice of claim 7, wherein the active layer is a photoactive layer. 15.The device of claim 14, wherein the active layer further comprises aphotoactive material.
 16. The device of claim 15, wherein thephotoactive layer consists essentially of the photoactive material and acopolymer having Formula I.
 17. A copolymer which is Compound A CompoundA